CN103500820B - A kind of sulphur for lithium-sulfur cell/porous carbon enveloped carbon nanometer tube composite positive pole and preparation method thereof - Google Patents
A kind of sulphur for lithium-sulfur cell/porous carbon enveloped carbon nanometer tube composite positive pole and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of sulphur for lithium-sulfur cell/porous carbon enveloped carbon nanometer tube composite positive pole and preparation method thereof, this lithium-sulfur battery composite anode material is composited by the porous carbon enveloped carbon nanometer tube complex carbon material and elemental sulfur with micro-nano structure; Poly-Abbado amine is first wrapped in carbon nano tube surface by preparation method, then by after high temperature carbonization, and elemental sulfur compound, to obtain final product; This preparation method is simple to operate, and cost is low, and obtained lithium-sulfur battery composite anode material utilization efficiency is high, substantially increases the cycle performance of lithium-sulfur cell.
Description
Technical field
The present invention relates to a kind of sulphur for lithium-sulfur cell/porous carbon enveloped carbon nanometer tube composite positive pole and preparation method thereof, belong to new energy field.
Background technology
Along with the extensive use of lithium ion battery in portable type electronic product, electric automobile and instant-plugging hybrid electric vehicle, in the urgent need to developing the battery of more high-energy-density.Be restricted because anode material for lithium-ion batteries specific capacity improves, the energy density of lithium ion battery is difficult to increase considerably further.Voltage platform simultaneously by increasing positive electrode improves energy density can bring safety issue again.Positive electrode is forwarded to " conversion reaction chemism " from " deintercalation mechanism ", is expected the material obtaining height ratio capacity and specific energy.Elemental sulfur is one of the most promising positive electrode, and sulphur generates Li with lithium metal complete reaction
2s, cell reaction is S+2Li=Li
2s is bielectron course of reaction, does not relate to the deintercalation reaction of lithium ion.Because the molecular weight of sulphur is low, the theoretical specific capacity of sulphur is up to 1675mAhg
-1(be almost LiFePO
410 times), theoretical specific energy is then up to 2600WhKg
-1.In addition, elemental sulfur is at nature rich reserves, low toxicity, cheap, and therefore elemental sulfur is a kind of positive electrode had a great attraction.
But there is the problems such as active material utilization is low, cycle performance is poor, the further raising of high rate performance needs in lithium-sulfur cell.And active material sulfur materials itself and final discharging product Li in lithium-sulfur cell
2s is the insulator of electronics and ion, and the intermediate product polysulfide in discharge process is soluble in electrolyte, and these can cause irreversible loss and the capacity attenuation of active material.For this reason, how to suppress the diffusion of polysulfide, improve the research emphasis that the distribution of sulphur and the conductivity improved in the cyclic process of sulphur positive pole are sulfur-based positive electrode materials.
For solving these problems of lithium-sulfur cell, at present normally by elemental sulfur load (filling, attachment, mixing, epitaxial growth, coated etc.) in the carbon element class material with high-specific surface area, high porosity and excellent conductive performance feature, form composite positive pole, to limit the various negative effects that polysulfide in cyclic process dissolves in electrolyte and causes thus.Wherein, carbon nano-tube has the advantages such as good conductivity, draw ratio be large, can be barricaded as natural conductive network by bridge, be conducive to the diffusion of electrical conductivity and lithium ion between them.In addition, the draw ratio that carbon nano-tube is large can strengthen collector, bonding agent and the intergranular engaging force of active material, produces positive meaning to stabilized electrodes structure.But the general specific area of traditional carbon nano-tube material is less, sulfur loaded limited in one's ability, cause that the sulfur content in the composite positive pole of preparation is low, skewness, be assembled into circulating battery after a few, still there is a large amount of active material sulphur can from the surface dissolution of carbon nano-tube, cause the loss of active material, lithium-sulfur cell energy density is difficult to improve further.If sulfur content promotes further in composite positive pole, a large amount of sulphur is distributed in the outer surface of carbon nano-tube, causes the conductive capability of electrode to decline on the one hand; The polysulfide that this part sulphur generates after electrode reaction on the other hand easily spreads and shuttles back and forth, and cause the irreversible loss of active material, the chemical property of material can not get good performance.
Through retrieval pertinent literature and patent, carbon nano-tube and elemental sulfur be 300 DEG C of hot compounds under vacuum, the sulfur content of the carbon nano-tube obtained/sulphur composite positive pole is 40wt.%, by the sulfur electrode that composite positive pole, conductive carbon black, bonding agent are made according to the mass ratio of 8:1:1, be assembled into lithium-sulfur cell and carry out constant current charge-discharge test discovery, after 100 circle circulations, capability retention also has 53.3%, and coulombic efficiency reaches 89%, embody excellent chemical property, but sulfur content is on the low side.（JuchenGuo,YunhuaXu,andChunshengWang.Sulfur-ImpregnatedDisorderedCarbonNanotubesCathodeforLithium-SulfurBatteries.NanoLett.2011,11,4288–4294）。In addition, carbon nano-tube/sulphur composite positive pole about high sulfur content also has report, after multi-walled carbon nano-tubes mixes than ball milling by the quality of 1:3 with elemental sulfur, 155 DEG C of melting compound 24h under an inert atmosphere, obtain the multi-walled carbon nano-tubes-sulphur composite positive pole of sulfur content 72.6wt.%, by composite positive pole, conductive carbon black, the sulfur electrode that bonding agent is made according to the mass ratio of 8:1:1, be assembled into lithium-sulfur cell and carry out constant current charge-discharge test under the current density of 100mA/g, discharge capacity has 1180mAh/g first, capacity only surplus 380mAh/g after 100 circle circulations, show that the chemical property of the carbon nano-tube/sulphur composite positive pole of high sulfur content is unsatisfactory.(MinHe,Li-XiaYuan,WuXingZhang,YunHuiHuang.Porouscarbonnanotubesimprovedsulfurcompositecathodeforlithium-sulfurbattery.JSolidStateElectrochem,201317:1641–1647)。Carbon nano-tube described above/sulphur composite positive pole all improves some chemical properties of lithium-sulfur cell, take full advantage of conductivity and the network configuration of carbon nano-tube, the restrictions such as but the character being limited to carbon nano-tube itself is as less in specific area, pore volume is low, the problem that carbon nano-tube/sulphur composite positive pole ubiquity sulphur load capacity is on the low side, this causes the specific capacity of sulfur electrode entirety less than normal, the problems such as energy density is low, are unfavorable for suitability for industrialized production.
Summary of the invention
The present invention is directed to that carbon nano-tube of the prior art/sulphur composite positive pole ubiquity sulphur load capacity is on the low side, and cause sulfur electrode specific capacity less than normal, the problems such as energy density is low, object is to provide one to have high positive active material utilization efficiency, can improve the sulphur/porous carbon enveloped carbon nanometer tube composite positive pole of lithium-sulfur cell cycle performance.
Another object of the present invention is the preparation method being to provide a kind of preparation simple to operate, that cost is low described sulphur/porous carbon enveloped carbon nanometer tube composite positive pole, and the method is suitable for suitability for industrialized production.
The invention provides a kind of sulphur for lithium-sulfur cell/porous carbon enveloped carbon nanometer tube composite positive pole, this composite positive pole is composited by the porous carbon enveloped carbon nanometer tube complex carbon material and elemental sulfur with micro-nano structure; Described porous carbon enveloped carbon nanometer tube complex carbon material is coated on by poly-dopamine through 500 ~ 1200 DEG C of high temperature carbonizations after carbon nano tube surface, the carbon-to-carbon organic combination that the carbon skeleton surface that the nanoporous carbon structure growth constructed by poly-dopamine obtained is constructed in carbon nano-tube is formed.
It is the polymerization reaction that dopamine occurs in solution by carbon nano-tube being joined containing dopamine that described poly-dopamine is coated on carbon nano tube surface, generates poly-dopamine rete realize in carbon nano tube surface.
Described poly-dopamine thicknesses of layers is 5nm ~ 100nm, and thickness is controlled by polymerization reaction time.
The specific area of described porous carbon enveloped carbon nanometer tube complex carbon material is 200 ~ 2000m
2/ g.
Described elemental sulfur spread loads is in the duct of porous carbon enveloped carbon nanometer tube complex carbon material inside and in the pore structure of the nanoporous carbon structure on surface; Described nanoporous carbon structure has the pore structure based on micropore, and mutually through between pore structure; Aperture≤the 2nm of described micropore, wherein, the ratio that micropore accounts for whole pore structure is 50 ~ 80%.
Described carbon nano-tube be Single Walled Carbon Nanotube, multi-walled carbon nano-tubes one or both; The diameter of described carbon nano-tube is 10nm ~ 200nm, and length is 500nm ~ 10 μm.
Present invention also offers a kind of preparation method of described composite positive pole, this preparation method is in the solution containing dopamine by carbon nano-tube ultrasonic disperse, under the condition stirred, slowly instill toward solution in pH be 8 ~ 10 alkaline solution carry out polymerization reaction; After having reacted, there is the carbon nano tube products of poly-dopamine to be placed in stove the Surface coating of gained, under an inert atmosphere, with the heating rate of 5 ~ 15 DEG C/min, temperature is risen to 500 ~ 1200 DEG C from room temperature, after insulation 5 ~ 20h; The porous carbon enveloped carbon nanometer tube complex carbon material obtained and elemental sulfur compound, to obtain final product.
The concentration range of described dopamine solution is 0.5 ~ 10mg/mL.
Described alkaline solution is KOH, NaOH, ammoniacal liquor, K
2cO
3, Na
2cO
3, K
3pO
4, Na
3pO
4one or more in solution.
The described one be complex as in ball-milling method, high-temperature hot melting, liquid phase in-situ deposition, liquid infiltration method.
Described dopamine is the analog of 3,4-dihydroxy-L-Phe.
The preparation process of lithium-sulfur cell sulphur of the present invention/porous carbon enveloped carbon nanometer tube composite positive pole: the carbon mano-tube composite presoma of the poly-dopamine clad surface of (1) preparation: carbon nano-tube being joined concentration is in the dopamine solution of 0.5 ~ 10mg/mL, after ultrasonic disperse process 1 ~ 5h, obtain suspension-turbid liquid; Under the condition of Keep agitation, in solution, slowly instillation PH is the dilute alkaline soln of 8 ~ 10, at room temperature stirring reaction 1 ~ 20h, the product deionized water of gained and ethanolic solution respectively wash for several times, obtain the carbon mano-tube composite presoma of poly-dopamine clad surface; (2) charing preparation has the porous carbon enveloped carbon nanometer tube complex carbon material of micro-nano structure: the carbon mano-tube composite presoma of poly-dopamine clad surface is transferred in tube furnace, under an argon atmosphere, with the heating rate of 5 ~ 15 DEG C/min, temperature is risen to 500 ~ 1200 DEG C from room temperature, insulation 5 ~ 20h, obtains porous carbon enveloped carbon nanometer tube complex carbon material; (3) compound prepares sulphur/porous carbon enveloped carbon nanometer tube composite positive pole, by the porous carbon enveloped carbon nanometer tube complex carbon material of (2) gained by the one in ball-milling method, high-temperature hot melting, liquid phase in-situ deposition, liquid infiltration method and elemental sulfur compound, to obtain final product.
Beneficial effect of the present invention: the present invention is devoted to the study on the modification of carbon nano-tube/sulphur positive electrode, the carbon nano-tube of obtained poly-dopamine clad surface first, method again in conjunction with high temperature carbonization obtains the porous carbon structure enveloped carbon nanometer tube complex carbon material with micro-nano structure, it is large that this complex carbon material carries sulfur content, and effectively can suppress polysulfide dissolving in the electrolytic solution, make it have the utilance of higher active material sulphur, substantially increase the cyclical stability of lithium-sulfur cell.Dopamine is slowly generated poly-dopamine by polymerization and is evenly coated on carbon nano tube surface by the present invention, again in conjunction with the method for high temperature carbonization, the carbon-to-carbon organic combination that the nanoporous carbon structure growth obtaining being constructed by poly-dopamine is formed on the carbon skeleton surface that carbon nano-tube is constructed; This carbon-to-carbon organic combination has the nano level hollow duct that poly-dopamine carbonizes the porous carbon structure based on micropore and carbon nano-tube itself existence of constructing simultaneously, these pore structures all maintain respective physicochemical characteristic, and it is mutually through between pore structure, make to obtain porous carbon enveloped carbon nanometer tube complex carbon material and there is higher porosity and larger specific area, considerably increase the load capacity (weight content reaches 55 ~ 85%) of elemental sulfur and the contact area of elemental sulfur, improve electron transfer rate and response area; Whole porous carbon enveloped carbon nanometer tube complex carbon material is perfect carbon-to-carbon organic combination simultaneously, maintains the good ion transport capability of carbon nano-tube and conductivity, for whole positive pole provides effective conductive network and lithium ion mobility passage; The simultaneously nanoporous carbon constructed of dopamine, the micropore of Nano grade reaches 50 ~ 80% of pore structure, the network duct of nanoscale effectively inhibits the dissolving diffusion of many lithium sulfides to run off, substantially increase the utilization ratio of active substances in cathode materials sulphur, be conducive to the raising of lithium-sulfur cell cyclical stability; In addition, the raw material sources that the present invention adopts are wide, and cheap, preparation method is simple to operate, cost is low, are applicable to suitability for industrialized production.
Accompanying drawing explanation
The SEM figure of the sulphur that [Fig. 1] obtains for embodiment 1/porous carbon enveloped carbon nanometer tube composite positive pole.
The discharge curve first of the sulphur that [Fig. 2] obtains for embodiment 1/porous carbon enveloped carbon nanometer tube composite positive pole and carbon nano-tube/sulphur composite positive pole.
The sulphur that [Fig. 3] obtains for embodiment 1/porous carbon enveloped carbon nanometer tube composite positive pole and carbon nano-tube/sulphur composite positive pole 100 circle cycle performance figure under 0.2C current density.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but is not restricted to the protection range of invention.Embodiment 1
By the Single Walled Carbon Nanotube of 1.0g, (diameter is 20nm, length is 1 μm) to join 200mL concentration be in the aqueous dopamine solution of 5mg/mL, under room temperature, ultrasonic process 2h obtains finely dispersed carbon nanotube suspension, then under the magnetic agitation continued, the NaOH solution of pH=9 is slowly instilled in suspension-turbid liquid, at room temperature after mechanic whirl-nett reaction 10h, products therefrom deionized water and ethanol are washed three times respectively, the impurity of removing its surface and dopamine monomer, obtain poly-dopamine coated carbon nano-tube composite material.A certain amount of poly-dopamine coated carbon nano-tube composite material is transferred in tube furnace; under the protection of inert nitrogen gas, with the heating rate of 10 DEG C/min, temperature is risen to 800 DEG C from room temperature; insulation 10h, obtains porous carbon enveloped carbon nanometer tube complex carbon material after charing.Find through BET test, the specific area of porous carbon enveloped carbon nanometer tube complex carbon material is by the 160m of original carbon nanotubes
2/ g is elevated to 802m
2/ g, the aperture≤2nm of micropore, the ratio that micropore accounts for whole pore structure is 70%.By porous carbon enveloped carbon nanometer tube complex carbon material and sulphur powder; with the mass ratio high speed ball milling mixing 2h of 2:8; then transfer in tube furnace; under the protection of inert gas argon gas; be warming up to 155 DEG C; insulation 24h, obtains sulphur/porous carbon enveloped carbon nanometer tube composite positive pole, tests its actual sulfur content is 72.5wt.% by thermogravimetric.As a comparison, original carbon nano-tube to be prepared according to the method described above close (71.8wt.%) carbon nano-tube/sulphur composite positive pole of sulfur content.Sulphur/porous carbon enveloped carbon nanometer tube composite positive pole preparation flow as schematic diagram as shown in Figure 1.Fig. 2 is the SEM figure of sulphur/porous carbon enveloped carbon nanometer tube composite positive pole, and as can be seen from Fig., sulphur is evenly distributed in whole composite positive pole.
The composite positive pole of embodiment 1 gained, conductive black, Kynoar (PVDF) are compared Homogeneous phase mixing according to the quality of 8:1:1, and be dispersed in the NMP of certain mass and do form slurry (solid content is 80wt%), then be coated in aluminum foil current collector, at 60 DEG C, obtain a kind of lithium-sulphur cell positive electrode sheet after vacuumize.
Battery assembling with test is: positive plate being struck out the electrode slice that diameter is 10mm, take metal lithium sheet as negative pole, and electrolyte is 1MLiTFSI/DOL:DME (1:1), is assembled into CR2025 button cell in the glove box being full of argon gas.Under room temperature, (25 DEG C) are with 0.2C(335mA/g) current density carry out constant current charge-discharge test, discharge and recharge cut-ff voltage is 1.5 ~ 3.0V.Relatively the chemical property of sulphur/porous carbon enveloped carbon nanometer tube composite positive pole and carbon nano-tube/sulphur composite positive pole, finds that they all show the typical discharge platform of lithium-sulfur cell, as shown in Figure 3.The former first discharge specific capacity is 1360mAh/g, and after 100 circulations, specific capacity keeps 700mAh/g, and the latter's first discharge specific capacity is 1200mAh/g, and after 100 circulations, specific discharge capacity is 400mAh/g, maintains the capability retention of 51.5% and 33.3% respectively.Sulphur/porous carbon enveloped carbon nanometer tube composite positive pole is compared to carbon nano-tube/sulphur composite positive pole, improves cyclical stability and the active material utilization of lithium-sulfur cell.
Embodiment 2
By the multi-walled carbon nano-tubes of 0.8g, (diameter is 100nm, length is 5 μm) to join 200mL concentration be in the aqueous dopamine solution of 0.5mg/mL, under room temperature, ultrasonic process 1h obtains finely dispersed carbon nanotube suspension, then under the magnetic agitation continued, the NaOH solution of pH=8 is slowly instilled in suspension-turbid liquid, at room temperature after mechanic whirl-nett reaction 8h, products therefrom deionized water and ethanol are washed three times respectively, the impurity of removing its surface and dopamine monomer, obtain poly-dopamine coated carbon nano-tube composite material.A certain amount of poly-dopamine coated carbon nano-tube composite material is transferred in tube furnace; under the protection of inert nitrogen gas, with the heating rate of 5 DEG C/min, temperature is risen to 1000 DEG C from room temperature; insulation 5h, obtains porous carbon enveloped carbon nanometer tube complex carbon material after charing.Find through BET test, the specific area of porous carbon enveloped carbon nanometer tube complex carbon material is by the 195m of original carbon nanotubes
2/ g is elevated to 1030m
2/ g, the aperture≤2nm of micropore, the ratio that micropore accounts for whole pore structure is 60%.By porous carbon enveloped carbon nanometer tube complex carbon material and sulphur powder; with the mass ratio high speed ball milling mixing 5h of 1:9; then transfer in tube furnace; under the protection of inert gas argon gas; be warming up to 155 DEG C; insulation 20h, obtains sulphur/porous carbon enveloped carbon nanometer tube composite positive pole, tests its actual sulfur content is 84.8wt.% by thermogravimetric.
Embodiment 3
By the Single Walled Carbon Nanotube of 1.5g, (diameter is 10nm, length is 500nm) to join 100mL concentration be in the aqueous dopamine solution of 10mg/mL, under room temperature, ultrasonic process 3h obtains finely dispersed carbon nanotube suspension, then under the magnetic agitation continued, the KOH solution of pH=8 is slowly instilled in suspension-turbid liquid, at room temperature after mechanic whirl-nett reaction 5h, products therefrom deionized water and ethanol are washed three times respectively, the impurity of removing its surface and dopamine monomer, obtain poly-dopamine coated carbon nano-tube composite material.A certain amount of poly-dopamine coated carbon nano-tube composite material is transferred in tube furnace; under the protection of inert nitrogen gas, with the heating rate of 15 DEG C/min, temperature is risen to 1200 DEG C from room temperature; insulation 8h, obtains porous carbon enveloped carbon nanometer tube complex carbon material after charing.Find through BET test, the specific area of porous carbon enveloped carbon nanometer tube complex carbon material is by the 120m of original carbon nanotubes
2/ g is elevated to 612m
2/ g, the aperture≤2nm of micropore, the ratio that micropore accounts for whole pore structure is 55%.By porous carbon enveloped carbon nanometer tube complex carbon material and sulphur powder; with the mass ratio high speed ball milling mixing 3h of 4:6; then transfer in tube furnace; under the protection of inert gas argon gas; be warming up to 155 DEG C; insulation 16h, obtains sulphur/porous carbon enveloped carbon nanometer tube composite positive pole, tests its actual sulfur content is 55.6wt.% by thermogravimetric.
Embodiment 4
By the multi-walled carbon nano-tubes of 2.0g, (diameter is 50nm, length is 10 μm) to join 200mL concentration be in the aqueous dopamine solution of 8mg/mL, under room temperature, ultrasonic process 4h obtains finely dispersed carbon nanotube suspension, then, under the magnetic agitation continued, in suspension-turbid liquid, the Na of pH=9 is slowly instilled
2cO
3solution, at room temperature after mechanic whirl-nett reaction 12h, washs three times respectively by products therefrom deionized water and ethanol, and the impurity of removing its surface and dopamine monomer, obtain poly-dopamine coated carbon nano-tube composite material.A certain amount of poly-dopamine coated carbon nano-tube composite material is transferred in tube furnace; under the protection of inert nitrogen gas, with the heating rate of 6 DEG C/min, temperature is risen to 850 DEG C from room temperature; insulation 2h, obtains porous carbon enveloped carbon nanometer tube complex carbon material after charing.Find through BET test, the specific area of porous carbon enveloped carbon nanometer tube complex carbon material is by the 180m of original carbon nanotubes
2/ g is elevated to 1980m
2/ g, the aperture≤2nm of micropore, the ratio that micropore accounts for whole pore structure is 80%.By porous carbon enveloped carbon nanometer tube complex carbon material and sulphur powder; with the mass ratio high speed ball milling mixing 4h of 3:7; then transfer in tube furnace; under the protection of inert gas argon gas; be warming up to 155 DEG C; insulation 12h, obtains sulphur/porous carbon enveloped carbon nanometer tube composite positive pole, tests its actual sulfur content is 68.5wt.% by thermogravimetric.
Embodiment 5
By the Single Walled Carbon Nanotube of 1.2g, (diameter is 15nm, length is 2 μm) to join 500mL concentration be in the aqueous dopamine solution of 1mg/mL, under room temperature, ultrasonic process 5h obtains finely dispersed carbon nanotube suspension, then, under the magnetic agitation continued, in suspension-turbid liquid, the KHCO of pH=10 is slowly instilled
3solution, at room temperature after mechanic whirl-nett reaction 6h, washs three times respectively by products therefrom deionized water and ethanol, and the impurity of removing its surface and dopamine monomer, obtain poly-dopamine coated carbon nano-tube composite material.A certain amount of poly-dopamine coated carbon nano-tube composite material is transferred in tube furnace; under the protection of inert nitrogen gas, with the heating rate of 8 DEG C/min, temperature is risen to 500 DEG C from room temperature; insulation 12h, obtains porous carbon enveloped carbon nanometer tube complex carbon material after charing.Find through BET test, the specific area of porous carbon enveloped carbon nanometer tube complex carbon material is by the 120m of original carbon nanotubes
2/ g is elevated to 320m
2/ g, the aperture≤2nm of micropore, the ratio that micropore accounts for whole pore structure is 50%, and specific area and pore volume are obtained for significant raising.By porous carbon enveloped carbon nanometer tube complex carbon material and sulphur powder; with the mass ratio high speed ball milling mixing 6h of 2:8; then transfer in tube furnace; under the protection of inert gas argon gas; be warming up to 155 DEG C; insulation 48h, obtains sulphur/porous carbon enveloped carbon nanometer tube composite positive pole, tests to obtain its actual sulphur sulfur-bearing 70.8wt.% by thermogravimetric.
Claims (10)
1. for sulphur/porous carbon enveloped carbon nanometer tube composite positive pole of lithium-sulfur cell, it is characterized in that, be composited by the porous carbon enveloped carbon nanometer tube complex carbon material and elemental sulfur with nanostructure; Described porous carbon enveloped carbon nanometer tube complex carbon material is coated on by poly-dopamine through 500 ~ 1200 DEG C of charings after carbon nano tube surface, the carbon-to-carbon organic combination that the carbon skeleton surface that the nanoporous carbon structure growth constructed by poly-dopamine obtained is constructed in carbon nano-tube is formed.
2. composite positive pole according to claim 1, it is characterized in that, it is the polymerization reaction that dopamine occurs in solution by carbon nano-tube being joined containing dopamine that described poly-dopamine is coated on carbon nano tube surface, generates poly-dopamine rete realize in carbon nano tube surface.
3. composite positive pole according to claim 2, is characterized in that, described poly-dopamine thicknesses of layers is 5nm ~ 100nm, and thickness is controlled by polymerization reaction time.
4. composite positive pole according to claim 1, is characterized in that, the specific area of described porous carbon enveloped carbon nanometer tube complex carbon material is 200 ~ 2000m
2/ g.
5. composite positive pole according to claim 1, is characterized in that, described elemental sulfur spread loads is in the duct of porous carbon enveloped carbon nanometer tube complex carbon material inside and in the pore structure of the nanoporous carbon structure on surface; Described nanoporous carbon structure has the pore structure based on micropore, and mutually through between pore structure; Aperture≤the 2nm of described micropore, wherein, the ratio that micropore accounts for whole pore structure is 50 ~ 80%.
6. composite positive pole according to claim 1, is characterized in that, described carbon nano-tube be Single Walled Carbon Nanotube, multi-walled carbon nano-tubes one or both; The diameter of described carbon nano-tube is 10nm ~ 200nm, and length is 500nm ~ 10 μm.
7. the preparation method of the composite positive pole according to any one of claim 1 ~ 6, it is characterized in that, by carbon nano-tube ultrasonic disperse to containing in the solution of dopamine, under the condition stirred, slowly instill toward solution in pH be 8 ~ 10 alkaline solution carry out polymerization reaction; After having reacted, there is the carbon nano tube products of poly-dopamine to be placed in stove the Surface coating of gained, under an inert atmosphere, with the heating rate of 5 ~ 15 DEG C/min, temperature is risen to 500 ~ 1200 DEG C from room temperature, after insulation 5 ~ 20h; The porous carbon enveloped carbon nanometer tube complex carbon material obtained and elemental sulfur compound, to obtain final product.
8. preparation method according to claim 7, is characterized in that, the concentration range of described dopamine solution is 0.5 ~ 10mg/mL.
9. preparation method according to claim 7, is characterized in that, described alkaline solution is KOH, NaOH, ammoniacal liquor, K
2cO
3, Na
2cO
3, K
3pO
4, Na
3pO
4one or more in solution.
10. preparation method according to claim 7, is characterized in that, the method for porous carbon enveloped carbon nanometer tube complex carbon material and elemental sulfur compound is the one in ball-milling method, high-temperature hot melting, liquid phase in-situ deposition, liquid infiltration method.
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| CN102142554A (en) * | 2011-02-16 | 2011-08-03 | 中国人民解放军63971部队 | Nano carbon sulfur composite material with network structure and preparation method of nano carbon composite material |
| CN102447113B (en) * | 2011-12-12 | 2014-08-13 | 南开大学 | Lithium battery with polymer-coated sulfur/carbon composite material as anode |
| CN103151524A (en) * | 2013-03-04 | 2013-06-12 | 北京化工大学常州先进材料研究院 | Positive pole material for high-performance lithium-sulfur battery and preparation method thereof |
| CN103258990B (en) * | 2013-04-24 | 2015-08-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Lithium sulfur battery anode material and preparation method thereof |
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